CN105924653A - Organic metal zinc (II) coordination polymer luminescent material and preparing method thereof - Google Patents
Organic metal zinc (II) coordination polymer luminescent material and preparing method thereof Download PDFInfo
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- CN105924653A CN105924653A CN201610298842.9A CN201610298842A CN105924653A CN 105924653 A CN105924653 A CN 105924653A CN 201610298842 A CN201610298842 A CN 201610298842A CN 105924653 A CN105924653 A CN 105924653A
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- coordination polymer
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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Abstract
The invention discloses an organic metal zinc (II) coordination polymer luminescent material and a preparing method thereof. The coordination polymer has the following repeated structure unit [Zn(mba)(bipy)(HCOO)], wherein mba represents 4-methoxy-benzoate anion, and bipy represents 2,2'-dipyridyl. The preparing method includes the steps that a water solution containing zinc sulfate, 4-methoxy benzoic acid, 2,2'-dipyridyl, formic acid and sodium hydroxide is put into a sealed reaction kettle to be subjected to hydrothermal reaction, the product is cooled to room temperature and filtered, and obtained filter liquor is volatilized and crystallized to obtain zinc (II) coordination polymer single crystal. The preparing method is easy to operate, mild in condition and high in yield; the prepared coordination polymer has an extremely strong fluorescence-emission peak (lambda ex=310 nm) at 327 nm position and can be used for preparing a luminescent device.
Description
Technical field
The present invention relates to a kind of organic metal zinc (II) coordination polymer luminescent material and preparation method thereof, belong to
Luminescent material synthesis field.
Technical background
Luminescent material is divided into phosphor and the big class of luminous organic material two.These materials have been widely used
In communication, satellite, radar, show, record, the high-tech area such as optical computer, probe biomolecule.
Wherein organometallic complex luminescent material owing to having that fluorescence quantum efficiency is higher, good film-forming property, be prone to purify,
The features such as fusing point is higher, character is relatively stable, and organic molecule is of a great variety, the beneficially design and assembly of luminescent material,
Thus such material is increasingly subject to the concern of researcher.Therefore, the organometallic complex of design synthesizing new is sent out
Luminescent material, studies its luminescent properties, and the relation between structure and luminosity of probing into has become Coordinative Chemistry, material
The problem that the fields such as material science are the most popular.
From 1987, Kodak C.H.Tang et al. 8-hydroxyquinoline aluminum-AlQ3As luminescent layer
After being fabricated with organic electroluminescence devices, people are to organometallic complex luminescent material growing interest.Impact is joined
The many factors of compound luminescent properties, mainly has electronic configuration and energy level, coordination configuration, the coordination of central ion
Environment, part, and the external condition such as solvent, temperature.
The preparation of luminescent material is frequently with high temperature solid-phase sintering method, and this method is the most traditional, prepares light effect
Preferably, but energy consumption is high, and product easily lumps, and after pulverizing, illumination effect decay is the biggest；The sedimentation method, this method deficiency
Place be product luminosity not so good；Combustion method, this method has prospect very much, but the luminescent powder of synthesis is luminous strong
Degree and brightness are the most slightly better than solid sintering technology.
Summary of the invention
The defect existed for prior art, an object of the present invention is to be to provide one to have new ligands
Structure, and organic metal zinc (II) coordination polymer under ultraviolet excitation with hyperfluorescence emission peak is luminous
Material.
Another object of the present invention be to provide a kind of simple to operate, reaction condition is gentle, the system of low cost
The method of standby described organic metal zinc (II) coordination polymer luminescent material, product thing prepared by the method is mutually equal
Even, purity and productivity are the highest.
In order to realize above-mentioned technical purpose, the invention provides a kind of organic metal zinc (II) coordination polymer and send out
Luminescent material, has following constitutional repeating unit: [Zn (mba) (bipy) (HCOO)], mba is 4-methoxybenzene
Formate ion, bipy is 2,2 '-bipyridyl；
Belonging to monoclinic system, space group is P2 (1)/c；
Cell parameter is:α=90.00 °,
β=97.523 (2) °, γ=90.00 °, Mr=417.71,Z=8, μ (MoK α)=
1.456mm-1, F (000)=1712.
Present invention also offers a kind of side preparing described organic metal zinc (II) coordination polymer luminescent material
Method, the method be by sulfur acid zinc, 4-methoxybenzoic acid, 2, the water of 2 '-bipyridyl, formic acid and sodium hydroxide
Solution is placed in sealed reactor, reacts 2～3 days, be cooled to room temperature at a temperature of 120～140 DEG C, filters,
Gained filtrate is crystallized by volatilization, obtains zinc (II) coordination polymer.
Preferably scheme, zinc sulfate, 4-methoxybenzoic acid and 2, the mol ratio of 2 '-bipyridyl be 1～1.5:3～
4:1～2.
More preferably scheme, zinc sulfate concentration in described aqueous solution is 0.027～0.036mol/L.
Preferably scheme, in aqueous solution, the concentration of sodium hydroxide is 0.054～0.072mmol/L.
Preferably scheme, in aqueous solution, the concentration of formic acid is 0.054～0.072mmol/L.
Preferably scheme, volatilization crystallization process is: filtrate be contained in open-top receptacle, with the preservative film of band micropore
Close vessel port, make solvent the most slowly volatilize, to separating out a large amount of crystal.
The preservative film that the present invention uses is conventional commercially available preservative film, and the micropore on preservative film can be pricked by syringe needle
Hole.
Hinge structure, the Advantageous Effects that technical scheme is brought:
Organic metal zinc (II) coordination polymer of the present invention is by having d10Zinc (II) ion of electronic configuration
Assemble with electron conjugated more rigid ligand and constitute, there is one-dimensional catenary structure.And special coordination ring
Border, makes organic metal zinc (II) coordination polymer have bigger fluorescence property, at coordination polymerization substrate concentration is
1.0×10-5mol.L-1Time, at 310nm (λex) ultraviolet excitation under, at 327nm occur the strongest
Fluorescence emission peak, can be widely applied to prepare luminescent device.
Organic metal zinc (II) coordination polymer of the present invention is synthesized by single step reaction, has simple to operate,
The feature that mild condition is easily-controllable, and the product purity of preparation is high, productivity is high, product grain fine uniform, separates
Purify easily.
Accompanying drawing explanation
[Fig. 1] is the coordination environment figure of zinc (II) coordination polymer of embodiment 1 preparation；
[Fig. 2] is the one-dimensional catenary structure figure of zinc (II) coordination polymer of embodiment 1 preparation；
[Fig. 3] is zinc (II) the coordination polymer fluorescent emission figure at room temperature of embodiment 1 preparation.
Specific implementation method
Specific examples below is intended to further illustrate present invention rather than limits the claims in the present invention
Protection domain.
The ZnSO that the present invention uses4.7H2O, anisic acid (4-methoxybenzoic acid), bipy 2,2' bipyridyl, first
Acid etc. is commercially available chemical reagent.
The instrument that the present invention uses is: magnetic force thermostat water bath；Bruker APEX-II CCD type single crystal diffraction
Instrument；Gangdong, Tianjin technology & development Co. WGY210 type spectrofluorophotometer.
Embodiment 1
1, luminescent material [Zn (mba) (bipy) (HCOO)]nPreparation:
By the amount ratio of material it is: the raw material ZnSO of 1.5:3:24.7H2O (0.3mmol), anisic acid (0.6mmol)
With 2,2 '-bipyridyl (0.4mmol), be dissolved in 11mL water, add, 0.6mmolNaOH and
0.6mmolHCOOH, encloses reactant in reactor, is warming up to 140 DEG C, is incubated 3 days, then natural
Being cooled to room temperature, filter, Sheng filtrate, in open-top receptacle, is closed vessel port with the preservative film of band micropore, is made molten
Agent is the most slowly volatilized, and separates out clear crystal after 1 week.Productivity is 42.3%.
2, to material [Zn (mba) (bipy) (HCOO)]nCarry out crystal structure determination:
Draw materials the monocrystalline of a size of 0.28 × 0.20 × 0.18nm, at Bruker SMART APEX-II CCD
On type single crystal diffractometer, it is light source with graphite monochromatised MoK α (λ=0.071073nm) radiation, determines material
Mono-crystalline structures.WithScan mode, in 296 (2) K, collects in the range of 2.11≤θ >=25.01 altogether
17015 diffracted intensity data, wherein 6052 independent point diffractions (Rint=0.0342), the observable of I > 2 σ
Point diffraction 5448.Use SHELXL-97 program, by direct method analytic structure, with a complete matrix young waiter in a wineshop or an inn
Multiplication, to structure in addition refine, determines hydrogen atom position in structure cell with theoretical hydrogenation method.
Fig. 1 is the coordination environment figure of Zn (II) in material.Main bond distance, bond angle are shown in Table 1.Known by Fig. 1, join
The minimum asymmetric cell of compound 1 is containing 2 Zn2+Ion, 2 Zn2+There is identical coordination environment, be five
Coordination distorted trigonal bipyramidal configuration.Such as Zn (1) ion and mba-1 carboxyl oxygen atom (Zn-O bond distance:
0.2015 (3) nm), 2 nitrogen-atoms (Zn-N bond distance: 0.2131 (4)～0.2155 (4)) of 1 bipy and
2 HCOO-2 carboxyl oxygen atoms (Zn-O bond distance: 0.2021 (3)～0.2057 (3) nm), constitute five and join
The distortion trigonal biyramid configuration of position.Wherein O (5)Ⅰ, O (4) and N (2) be positioned at the equatoriat plane of trigonal biyramid, Zn (1)
Being positioned at equatorial plane, O (1), N (1) atom are positioned at the axial location of trigonal biyramid.It is positioned at equatorial plane
O (5)-Zn (1)-N (2), N (2)-Zn (1)-O (4), the bond angle of O (4)-Zn (1)-O (5) is respectively 93.56 (1)
°, 163.09 (1) °, 99.59 (1) °, total bond angle is 356.24 °, and 360.0 ° are deviateed 3.76 °, O (5) is describedⅠ、O(4)
The most coplanar with N (2).O (1)-Zn (1)-N (1) bond angle being in axial location is 154.88 (2) °, offset straight
Line angle 25.12 °, illustrates that above-mentioned trigonal biyramid distortion degree is bigger.The asymmetric list of adjacent minimum in complex crystal
Unit, passes through HCOO-The adjacent Zn of bridging (II) becomes one-dimensional catenary structure (see Fig. 2).
Table 1 [Zn (mba) (bipy) (HCOO)]nMain bond distanceWith bond angle (°)
Symmetry codes:Ⅰ:x,-y,-0.5+z；Ⅱ:x,1-y,-0.5+z
3, material [Zn (mba) (bipy) (HCOO)]nPhotoluminescent property measure:
Under room temperature, coordination compound is dissolved in methanol aqueous solution (volume ratio 1:1) so that it is concentration is 1.0 × 10-5
mol.L-1Time, at 310nm (λex) ultraviolet excitation under, the strongest fluorescent emission occurs at 327nm
Peak (see Fig. 3).Material fluorescence intensity of the present invention is much larger than coordination compound in document [1].[1] Yang Yingqun, Li Changhong,
Li Wei, etc. three core zine coordination compound Zn3(phen)2(2,4-DAA)6] Hydrothermal Synthesis, crystal structure, fluorescence
And electrochemical properties. SCI, 2008,29 (3): 49-452.
Embodiment 2
1, luminescent material [Zn (mba) (bipy) (HCOO)]nPreparation:
By the amount ratio of material it is: the raw material ZnSO of 1.2:3.2:1.84.7H2O (0.24mmol), anisic acid
(0.64mmol) He 2,2 '-bipyridyl (0.36mmol), be dissolved in 8mL water, add, 0.5mmolNaOH and
0.5mmolHCOOH, encloses reactant in reactor, is warming up to 120 DEG C, is incubated 3 days, then natural
Being cooled to room temperature, filter, Sheng filtrate, in open-top receptacle, is closed vessel port with the preservative film of band micropore, is made molten
Agent is the most slowly volatilized, and separates out clear crystal after 1 week.Productivity is 40.7%.Crystal coordination structure
Consistent with embodiment 1.
Claims (7)
1. organic metal zinc (II) coordination polymer luminescent material, it is characterised in that: there is following repetition and tie
Structure unit: [Zn (mba) (bipy) (HCOO)], mba is 4-methoxybenzoic acid radical ion, bipy is 2,2 '-
Bipyridyl；
Belonging to monoclinic system, space group is P2 (1)/c；
Cell parameter is:α=90.00 °,
β=97.523 (2) °, γ=90.00 °, Mr=417.71,Z=8, μ (MoK α)=
1.456mm-1, F (000)=1712.
2. the method for preparation organic metal zinc (II) coordination polymer luminescent material described in claim 1, it is special
Levy and be: by sulfur acid zinc, 4-methoxybenzoic acid, bipy 2,2' bipyridyl, formic acid and the aqueous solution of sodium hydroxide
It is placed in sealed reactor, reacts 2～3 days at a temperature of 120～140 DEG C, be cooled to room temperature, filter, institute
Obtain filtrate to be crystallized by volatilization, obtain zinc (II) coordination polymer monocrystalline.
The method of preparation organic metal zinc (II) coordination polymer luminescent material the most according to claim 2,
It is characterized in that: the mol ratio of zinc sulfate, 4-methoxybenzoic acid and bipy 2,2' bipyridyl be 1～1.5:3～4:1～
2。
The method of preparation organic metal zinc (II) coordination polymer luminescent material the most according to claim 3,
It is characterized in that: described zinc sulfate concentration in described aqueous solution is 0.027～0.036mol/L.
The method of preparation organic metal zinc (II) coordination polymer luminescent material the most according to claim 2,
It is characterized in that: in described aqueous solution, the concentration of sodium hydroxide is 0.054～0.072mmol/L.
The method of preparation organic metal zinc (II) coordination polymer luminescent material the most according to claim 2,
It is characterized in that: in described aqueous solution, the concentration of formic acid is 0.054～0.072mmol/L.
7. the preparation method of claim 2, it is characterised in that: described volatilization crystallization process is: filtrate be contained in
In open-top receptacle, close vessel port with the preservative film of band micropore, make solvent the most slowly volatilize, extremely
Separate out a large amount of crystal.
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| CN114149660A (en) * | 2021-11-27 | 2022-03-08 | 兰州交通大学 | Application and preparation method of organic zinc |
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